Synthesis and characterisation of highly branched polyisoprene: exploiting the “Strathclyde route” in anionic polymerisation

Copolymerisation of isoprene and divinylbenzene was achieved in tolueneviaanionic chain transfer polymerization to yield highly branched polymers with good solution and rheological properties.

Infinite Anionic Chains Formed by Alternating Bidentately Acting [SbS4]3- Anions and [Mn(dien)]2+ Complexes in the Compound [Mn(dien)2][Mn(dien)SbS4]2

The new compound [Mn(dien)2][Mn(dien)SbS4]2 (dien=diethylenetriamine) was synthesized under solvothermal conditions. It crystallizes in the non-centrosymmetric monoclinic space group P21 with a=7.5736(5), b=19.1081(16), c=13.1174(11) Å, b =90:022(9) , V =1898.3(3) Å3, and Z =2. The crystal structure is composed of one [Mn(dien)2]2+ cation and an anionic chain composed of [SbS4]3- anions and [Mn(dien)2]2+ cations. The [SbS4]3- anions connect [Mn(dien)2]2+ ions in a μ2-fashion to form an undulated {[Mn(dien)SbS4]}-2 chain running along [001]. The Mn2+ ions in the chain are in a rare distorted rectangular pyramidal coordination environment with 3 N and 1 S atom forming the base and one S atom being located at the apex of the pyramid. The anionic chains and the cations alternate along [010]. Several relatively strong intra- and inter-chain N-H-S bonding interactions are observed. From the Raman spectrum the reduction of the ideal Td symmetry of the [SbS4]3- anions is obvious because more resonances occur than expected for the undistorted geometry

catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato-κ2 O,O′)terbium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

In the title compound, {[Tb(NO3)2(C6H18N3OP)4][AgWS4]} n , the polymeric anionic chain {[AgWS4]−} n extends along [001]. The TbIII atom in the cation is coordinated by eight O atoms from two nitrate and four hexamethylphosphate ligands in a distorted square-antiprismatic geometry. Together with the two nitrate ligands, the cation is univalent, which leads to the anionic chain having a [WS4Ag] repeat unit. The polymeric anionic chain has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.49 (2) and 153.743 (13) °, respectively. The title complex is isotypic with the Y, Yb, Eu, Nd, La, Dy, Sm and Lu analogues.

catena-Poly[[tetrakis(hexamethylphosphoramide-κO)bis(nitrato-κ2 O,O′)lutetium(III)] [silver(I)-di-μ-sulfido-tungstate(VI)-di-μ-sulfido]]

In the title compound, {[Lu(NO3)2(C6H18N3OP)4][AgWS4]} n , hexamethylphosphoramide (hmp), tetrathiotungstate, silver iodide and lutetium nitrate were self-assembled, forming an anionic {[AgWS4]−} n chain extending parallel to [001]. The LuIII atom in the cation is coordinated by eight O atoms from two nitrate groups and four hmp ligands in a distorted square-antiprismatic geometry. Together with the two nitrate groups, the cation is monovalent, which leads to the anionic chain having a [WS4Ag] repeat unit. The polymeric anionic chain has a distorted linear configuration with W—Ag—W and Ag—W—Ag angles of 161.66 (2) and 153.503 (12)°, respectively. The title complex is isotypic with the Y, Yb, Eu, Nd, La, Dy and Sm analogues.